Process of rendering hydrophobic textile material antistatic and resulting product



United States Patent PROCESS OF RENDERING HYDROPHOBIC TEX- TILE MATERIAL ANTISTATIC AND RESULTING PRGDUCT Reginald L. Wakeman, Philadelphia, Pa., assignor, by mesne assignments, to Millmaster Onyx Corporation, New York, N .Y., a corporation of New York No Drawing. Filed Oct. 23, 1962, Ser. No. 232,574

24 Claims. (Cl. 117-1383) This invention relates to textile finishing agents. More particularly, it relates to amine-modified polymeric esters capable of being applied to textile fibers to provide durable finishes which enhance the valuable properties thereof, and a process for applying these finishes to fibers and fabrics.

This application is more specifically concerned with a modification of the subject matter of the assigned copending application Serial Number 102,910, filed on February 21, 1961, now US. Patent No. 3,063,870. In that earlier application, it is disclosed that certain amine modified polymeric esters could be cross linked on fabrics to produce finishes which resist laundering and dry cleaning by conventional commercial methods.

It has now been found that the amine-modified polymeric esters when not cross linked have important characteristics and applications in the finishing of textile fibers. The finishes produced are removable by laundering but are not impaired by repeated dry cleaning. The polymeric esters applied without cross linking form an anti-static finish which prevents accumulation of electric charges on hydrophobic textile fibers.

The products used as finishes in the present invention comprise polymeric esters of amino acids which are either Water-soluble or which may be made Water-soluble upon acidification. Although, under certain conditions, it is possible to prepare such amino polyesters by direct esterification of dibasic amino acids such as aspartic acid, glutamic acid, or their N-substituted alkyl homologs with polyhydric alcohols such as glycols or polyglycols (glycol polyethers), in general these compounds are preferably obtained by indirect means. For example, an alpha unsaturated dicarboxylic acid may be esterified with a glycol or polyglycol and the unsaturated polyester thus formed may then be reacted with ammonia or with a primary or secondary amine. The ammonia or amine adds across the double bond of the unsaturated ester, thus forming an amine-modified polyester. For example, 6 amino esters are formed by amination of unsaturated polyesters.

The reactions involved are represented by the following formulas:

wherein n is at least 2, and preferably between 2 and 8; R is either the radical of a glycol HO(CHfl -OH (V) or of a polyglycol HO[ (CH -O] (CH ---OH (VI) Rand R" are each hydrogen, alkyl, or substituted alkyl radicals; n is an integer between 2 and 10' m and m" are integers between 2 and 10.

Formulas I1 and IV above respectively represent one ester unit of a polymeric unsaturated ester and of a polymeric amino substituted ester of the invention.

3,181,969 Patented May 4, 1965 ice Alpha unsaturated dibasic acids which may be used in preparing the intermediate unsaturated polyesters include maleic acid or its anhydride, fumaric acid, itaconic acid, mesaconic acid, citraconic acid and glutaconic acid. Any otheralpha unsaturated dicarboxylic acid such as itaconic acid, glutaconic acid, mesaconic acid, citraconic acid and the like may be employed, preferably one containing between four and ten carbon atoms in the molecule. Hexene-2-dicarbonic acid, ethyl maleic, a,fi-dimethyl glutaconic acid, xeronic acid and iso amyl glutaconic acid are examples of organic acids containing between six and ten carbon atoms and used in accordance with my invention. Mixtures of these acids may be employed and mixtures thereof with such saturated dibasic acids as succinic acid, sebacic acid, phthalic acid and the like may also be used.

Glycols and glycol ethers which may be used in preparing the intermediate unsaturated polyesters include ethylene glycol, the propylene glycols, the butylene glycols, the pentanediols, diethylene glycol, polyethylene glycols, such as polyethylene glycol 200, polyethylene gylcol 400, polyethylene glycol 600, polyethylene glycol 1540 known under the trade name of Carbowax 1540, a trademark of Union Carbide Chemicals Co., neopentyl glycol and mixed polyglycols containing two or more alkylene radicals such as those which can be derived by conjoint polymerization of ethylene oxide and propylene oxide. We may also use substitution products of the aforementioned glycols in which one or more hydrogen atoms attached to carbon are replaced, for example, by alkyl groups containing from one to four carbon atoms. Mixtures of these glycols may also be employed.

The chain propagation of polyesters so prepared may be limited, i.e., the further growth of the polymeric group may be interrupted by some chemical which terminates the chain at a reactive site, by any method known to the art, such as by use of a monohydric alcohol, a monobasic acid, or a monoamine in suitable amount during the esterification reaction.

In general, I may use glycols or polyglycols containing from two to ten carbon atoms in the alkylene radical thereof. I may use glycols such as hexylene glycol and decamethylene glycol, and, in general prefer those glycols or polyglycols which will yield water-soluble products rather than water-dispersible ones. Hence, a preferred embodiment of my invention utilizes polyethylene glycols having a molecular weight of from about 200 to about 1540.

If desired, a polyester which is not of unsaturated nature, but which contains reactive hydrogens, may also be employed for introduction of an amine group by means, for example, of the amino methylation reaction known as the Mannich synthesis. Thus, for example, a polyglycol ester of malonic acid may be used and the active hydrogen of the malonic acid radical may be replaced in Whole or in part by an alkyl or aralkyl aminomethyl radical or by a corresponding disubstituted amino radical derived from monoamines or polyamines containing either primary or secondary amino groups and formaldehyde as hereinafter shown in Example 20.

Amino com-pounds which are suitable for introduction into polyesters according to this invention include aliphatic primary amines such as methyl amine, ethyl amine, propyl amine, isopropyl amine, butyl amine, hexyl amine, Z-ethyl hexyl amine, decyl amine, lauryl amine, stearyll amine and others, aliphatic secondary amines such as dimet hy l amine, die-thyl amine, diisopropyl amine, di-Q-ethyl hexyl amine, dilauryl amine, distea-ryl amine and others, aliphatic alkylene and poly alkylene polyamines such as ethylene diamine, propylene diamine, l,3-diamino propane, diethylene triam-ine, triethylene tetramine, tetraethylene pentamine, 3,3-bis-amino propylamine, and condensation products of the above-mentioned 'al-kylene and polyalkylene polyamines with fatty acids such as butyric acid, octoio acid, lauric acid, palmitic acid, stear-ic acid or oleic acid. These condensation products may be either amino alkylene amides of the fatty acids employed or they may be alkyl imidazolines formed by ring closure of these amides by continued dehydration.

Aliphatic unsaturated amines such as allyl amine and crotyl amine may be likewise employed if desired. Hydroxyl substituted aliphatic "amines may also be used such as monoethanolamine, diethanolamine, and amino ethylethanolamine.

Cycloaliphatic amines may also be employed such as cyclo'hexyl amine and dicyclohexyl amine. It is thus apparent that the amines which may be used in the present invention include a wide diversity of compounds of the aliphatic and cycloaliphatic series. Aralkyl ammes may also be employed, such for example, as benzyl amine and the like. Mixtures of amines may also be used. Amines suitable for the purposes of this invention are limited only by their ability to yield water-dispersible or water-soluble products. In general, however, they should contain from 1 to 26 carbon atoms. To use amines having a higher carbon content would render the products too difiicult to dissolve or disperse in water. Moreover, we prefer to employ those amines possessing from one to four carbon atoms and from one to three amino groups.

Although reference has been made specifically to amino modified polybasic acids as the essential components of the amino polyesters that are employed by the process of this invention, polyesters derived either in whole or in part rtrom saturated dibasic acids which are modified in turn by one or more monobasic aliphatic alpha-unsaturated acids, such for example, as acrylic acid, methacrylic acid or crotonic acid may :be used. In such cases, the amines hereto-fore mentioned are added across the double bond of the monobasic a'cid radical, in the same way as previously described with respect to the unsaturated dibasic acids. In such instances also, the monobasic unsaturated acids may be present as monoesters or diesters or polyesters of polyhydric compounds bearing two residual hydroxyl groups capable of further resinification, such for example, as the monoacrylate of glycerine, the monomethacrylate of trimethylol propane, the monoacrylate of trimethylol propane, the dicrotonate of pentaerythritol or the diacrylate of an ethylene oxide adduct of pentaerythritol.

The following examples illustrate the preparation of intermediate polymeric unsaturated esters to which amines may be added for the purposes of this invention:

Example 1 Example 2 100 parts of maleic anhydride and 400 parts of polyethylene glycol 400 were reacted during 14 hours at 127 130 C. using 1.5 parts of methane sulfonic acid and 150 parts of toluene to remove water as an azeotrope. It is to be noted that instead of using 400 parts of polyethylene glycol 400, 1600 parts of Carbowax 1540 may be used.

Example 3 607 parts of polyethylene glycol 600, 98 parts of maleic an'hydride and 1.3 parts of methane sulfonic acid were reacted under azeotropic conditions in the presence of 194 parts of toluene. Reflux was carried out at 128 -130 C. ttor 11 hours and water and toluene removed as in "Example l.

4 Example 4 416 grams of ethylene glycol and 792 grams of tumaric acid were heated while sparging with nitrogen until a maximum temperature of 230 C. had been attained. The product was a viscous liquid having a light yellow color.

Example 5 550 grams of diethylene glycol and 675 grams of itaconic acid were reacted with carbon dioxide as a sparging gas to a maximum temperature of 230 C. Upon cooling, the product was a very viscous, light amber liquid.

Instead of the maleic anhydride used in the preceding examples, we may use equimolar amounts of other alpha unsaturated d-icarboxylic acids such as mesaconic, citraconic or glutaconic acid.

Example 6 200 parts of polyethylene glycol 200, parts of succinic anhydride and 26 parts of crotonic acid were reacted as in Example 1, the product being a viscous, dark yellow liquid. Instead of crotonic acid an equal amount of methacrylic acid may be used. If desired, acrylic acid can also be used to replace the crotonic acid of this example in equivalent amount. Instead of succinic anhydride, 126 parts of phthalic anhydride may be employed.

Example 7 490 parts of maleic anhydride were reacted with 520.5 parts of pentanediol-1,5 in the presence of 10.1 parts of methane sulfonic acid under reduced pressure (30-33 mm.) at a temperature ranging from 80 C." C. during 5 hours. Water was removed during the operation and the product was a light colored, viscous liquid, insoluble in water but soluble upon acidification.

Examples 8 through 19 show the preparation of aminosubstituted polymeric esters from the unsaturated polyesters of the preceding examples.

Example 8 To the product of Example 1, 37 parts of diethyl amine was added at 70 C. through a separatory funnel in a dropwise manner. After addition of all of the diethyl amine, the temperature was raised to 110 C. and held for 2 hours. Unreacted diethyl amine was then removed at 10 millimeter vacuum, raising the temperature to C. during one-half hour. 3 parts of unreacted diethyl amine was removed in this manner. The product was a dark brown, very viscous, water-soluble liquid.

Example 9 37 parts of diethyl amine was added as in Example 8 to the product of Example 2, yielding a dark brown, viscous, water soluble liquid somewhat lighter in color than the product of Example 1.

Example 10 37 parts of diethyl amine was added to the product of Example 3 under the same conditions as given in Example 8. The product was a light brown, very viscous, water-soluble liquid somewhat lighter in color than the product of Example 9.

Example 11 33 parts of methyl amine gas was passed into 200 parts of the product of Example 4 at a temperature of 30 C. The temperature of reaction rose rapidly to about 80 C. The mixture was stirred after completion of addition of monomethyl amine for a period of one and one-half hours. The product has a molasses-like viscosity and could be dissolved in water by addition of a small amount of acetic acid or hydrochloric acid.

Instead of the methyl amine, 18 parts of anhydrous ammonia may be used to yield a similar product.

Example 12 93 parts of cyclohexyl amine was reacted with 190 parts of the product of Example 4 under the conditions of Example 10, the product being a very viscous, amber colored liquid which could be dissolved in water by acidification.

Example 3 40 parts of an alkyl imidazoline which was prepared by condensing double-pressed stearlc acid with diethylene triamine in an equimolar ratio with removal of two mols of water was reacted with 90 parts of the product of EX- ample 3 at a temperature of 75-100 C. After one hour of reaction, the product was cooled and was of an orange reddish color, semi-solid in nature, soluble in acidified isopropyl alcohol-water mixture.

Example 14 300 parts or dipropylene glycol, 200 parts of diethylene glycol and 400 parts of maleic anhydride were reacted in a manner similar to that of Example 4. To 200 parts of the product was added, under the conditions of Example 13, 30 parts of an imidazoline prepared from equimolar amounts of butyric acid and diethylene triamine. The product was a dark brown, viscous, water soluble fluid.

Example 15 250 parts of the product of Example 5 was reacted with 40 parts or" monoethanolamine under the conditions of Example 12. A viscous, orange-brown fluid was obtained.

Example 1 6 202 parts of the product of Example 7 was reacted with 36.4 parts of diethyl amine added drop-wise during onehalf hour at 60 C. Reaction was then continued for one and one-half hours longer at 120 C. A 15 mm. vacuum was applied at 120 C. during one and one-half hours, thus removing 3.6 parts of unreacted diethyl amine. The product or" this reaction was a water-insoluble, light yellow solid which, upon acidification with acetic acid or hydro chloric acid became water-soluble.

Example 17 202 parts of the product of Example 7 was reacted with 14.6 parts of dicthyl amine under the same conditions as in Example 16. 1 part of unreacted amine was removed at reduced pressure. The product was a very light colored solid, water-insoluble, but becoming soluble upon the addition of acid.

Example 18 553 parts of the product of Example 2 was reacted with 14.6 parts of diethyl amine as shown in Example 17, with final removal of 1 part of diethyl amine. The product was a dark viscous, water-soluble liquid.

Example 19 To the product of Example 6, was added 13 parts of dimethyl amine, anhydrous, with cooling. After addition of all the amine, the reaction mixture was allowed to come to room temperature and stand for 24 hours. The product was a dark colored, viscous, water-soluble fluid.

It is to be understood that the preceding examples are illustrative of the wide diversity of types of chemical compounds which may be used in the process of the invention described hereinafter. Any of the acids, glycols and amines previously mentioned may be employed in making finishes suitable for the process of this invention.

In general, the esters to which the amineis added should be relatively low in acid number. I prefer to use esters having an acid number of 30 or less. The esters should be as nearly neutral as possible. If the degree of acidity of the polyester exceeds an acid number of 30, too much amine will be consumed in making an amine salt. The amount of amine added should not exceed the amount of residual acid of the ester plus the urisaturation in the chain. Likewise, the amount of amine added must be in excess of the amount of residual acidity to be neutralized, but should not exceed the molecular equivalents of the unsaturation present in the chain. A portion or all of the unsaturation may be utilized by amino addition; that is to say, in a polyester containing four double bonds, for example, from one to four mols of amine may be added, as desired, to one mol of polyester.

The following example illustrates the preparation of a suitable amino-polyester from malonic acid by the Mannich reaction:

Example 20 104 parts of malonic acid, 400 parts of polyethylene glycol 400 and 2.5 parts of toluene sulfonic acid were added to a three-neck reaction flask fitted with agitator and heated to 140 C. at 20 mm. vacuum. Water vapor removed from the reaction was collected in a condenser :ooled with an ice calcium chloride mixture. After 10 hours, 16 parts of water had been collected, indicating 89% reaction.

To the polymeric ester produced, 15 parts of paraformaldehyde and 10 parts of hydrochloric acid were added at 60 C. 22.5 parts of anhydrous dimethyl amine was then passed under the surface, while stirring, during one and one half hours at 60 C. At the end of this time, analysis of unreacted formaldehyde showed 90% reaction. The product, a polymeric ester possessing dimethylamino methylene groups replacing hydrogen of the methylene radicals of the malonic acid, was a yellow-colored, viscous, water-soluble paste.

The substantially linear amino polyesters formed according to the preceding description and in accordance with the illustrations of Examples 8 to 20 can be employed for imparting an anti static finish to textile material in a manner which will be illustrated hereinafter. The finish is highly resistant to commercial drycleaning, but can be removed by normal wet laundering procedures.

The goods are impregnated and once treated, are dried at temperatures of approximately 200400 R, depending upon time, which may vary from periods of approximately 30 minutes near the lower temperature limit to a few seconds at the higher temperatures.

The compounds of this invention when properly applied to hydrophobic textile materials, act as durable anti static finishes, extremely resistant to drycleaning. The appearance and hand of the cloth are not unfavorably affected by the finish. It is moveover, possible to impart a wide range of properties to the treated cloth (e.g. stiffness, softness, body) by adequately choosing raw materials for the finish applied.

An adequate measure of the ability of the textiles to dissipate charges is their electrical conductivity (or electrical resistivity which is the reciprocal value of conductivity). It is known that a specific area conductance of the textile material higher than 10 reciprocal ohrn (i.e., an area resistivity lower than 10 ohms) is sufil cient to consider the textile material as having no objectionable tendency for the accumulation of charges. A higher specific area resistance is usually indicative of the tendency to accumulate charges.

I define the area resistivity of the fabric as its electrical resistance between two parallel metallic electrodes placed at a distance equal to their length. When the distance between electrodes is n times their length, the measured resistance must be divided by n in order to obtain the specific area resistance. The instruments used to measure electrical resistance are well lmown, e.g. a Wheatstone bridge may be used, or a strip of fabric is placed between electrodes connected across a device for measuring electric potential (voltage) having a very high leakage resistance and a potential is then applied across the fabric; the source of potential is then disconnected from the electrodes. From the observed rate of discharge of the iniarea resistivity can be calculated.

The electric resistance of textile materials depends on their moisture content, which in turn is a function of the relative humidity of the surrounding atmosphere. T herefore, measurement of electrical resistivity of the fabric must be carried out at a known relative humidity level in order to give reproducible results. The measurements indicated in the following examples were carried out at a relative humidity of substantially 30% and at 74 F.

The treatment of textiles by the process of this invention is illustrated by the following Examples 21 and 22. It will be understood that the invention is not limited to the details of these examples, but embraces equivalent processes as described herein, within the limits of processing conditions hereinafter set forth.

Example 21 An undyed, bleached taffeta fabric Woven from Dacron polyester yarn was impregnated in a three-roll padder with an aqueous solution containing 100 parts of water and 16 parts of the product of Example 11, acidified with formic acid to a pH of 6.5. The cloth was dried for two minutes at 220 F. and then heated four minutes at 250 F. The dry pickup or add-on was found to be 2 parts per 100 parts of fabric by weight. The treated fabric showed a specific area resistance in the order of 10 ohms after 10 commercial dry cleaning cycles. A portion of the same fabric which had not been treated in the manner described showed a specific area resistance greater than 10 ohms. The treated fabric, after many dry cleanings, thus exhibited no objectionable tendency to accumulate electrostatic charge, 10 ohms being a practical dividing line between comfort and discomfort for wearing apparel, with respect to the acquisition of static electricity.

Example 22 An undyed, bleached taffeta fabric woven from Dacron polyester yarn was impregnated on a three roll padder with an aqueous solution containing 100 parts of water and 16 parts of the product of Example 11, acidified with formic acid to a pH of 6.5. The cloth was dried for two minutes at 220 F. The fabric was then transferred to an oven maintained at 250 F., and removed therefrom after five minutes. The dry pick-up or add-on was found to be 2 parts per 100 parts of fabric by weight. The treated fabric showed a specific area resistance of approximately 10 ohms after ten commercial dry cleaning cycles in perchloroethylene.

Example 23 A textile treating bath was prepared containing 8 parts of the product of Example 8 dissolved in 92 parts of water and adjusted to a pH of about 6. Dacron taffeta was passed through this solution in a padder to a 20% wet pickup and dried at 200 F. for minutes. The dried fabric contained 2% of added solids on the weight of the goods. It was subsequently cured during 4 minutes at 250 F.

Initial specific area resistance of the treated fabric was ohms. Area resistance was not significantly reduced by ten commercial dry cleaning cycles using Stoddard solvent. Untreated fabric possessed a specific area resistance between 10 and 10 ohms regardless of the number of dry cleaning cycles.

Example 24 A textile treating bath was prepared in a manner similar to that of Example 23 using the product of Example 9. Dacron taffeta was similarly treated to a dry add-on of 2% by weight of the fabric. Drying and curing conditions were the same as in Example 23. The fabric after curing showed an initial specific area resistance of 10 ohms. This resistance is not significantly increased by dry cleaning.

The fabrics treated by the processes of Examples 21, 22 and 23 lose their anti static finish if laundered even once under the conditions customary in commercial practice.

Example 25 A product essentially the same as that set forth in Example 9 is obtained by the reaction of 553 grams of polyethylene glycol 400, about 125 grams of maleic anhydride and 36.4 grams of diethyl amine. After the reaction is complete there are removed four parts of amine at the end of the reaction.

This product gives an anti static finish durable to dry cleaning when applied without any catalyst or curing. Applications were made to a commercial 70% Acrilan/ 30% wool worsted, drying four minutes at 250 F. The log resistivity (R) of the treated fabric after fifteen dry cleanings amounted to 11.7.

It will be apparent that any of the products of Examples 8 to 20 may be employed for the treatment of textiles in accordance with the processes of Examples 21 to 25, as applicable. In general, we may use a textile treating bath containing from about 1% by weight of amino polyester to about by Weight thereof. I prefer to employ from about 5% to about 12%. In general, also, I may use a dry add-on of from about /2% on the weight of the goods to about 8% on the weight of the goods. I prefer to use between from about 1% to about 3%. The pH of the textile treating bath may vary from about 4 to about 11. In general, I prefer to use from about 6 to about 9.

In general, I may use any of the hydrophobic fibers herein above set forth. All hydrophobic fibers behave similarly since the phenomenon is presumably attributable to surface deposition. Where it is desired to reduce the anti static charge which can be acquired by woolen or giixed goods such as in carpeting, we may also use wool bers.

Blends of any of the preceding fibers may be employed and application may be made to woven or non-Woven goods, to tufted and pile fabrics and to knitted goods, felted goods and fibers, both staple and filament.

Application of the anti static finishes according to the process of this invention may be made from a padder, from a jig, from a dyebox, by spray, or by any other appropriate means.

It will be understood that treatment of textile fibers or fabrics according to the process of this invention may be carried out with addition to the bath of any desired surfactant or textile finish or dye which may be compatible with the anti static agents of the present invention.

While a preferred method and products are disclosed and exemplified herein, it is understood that various changes as to procedure, arrangement and use of materials may be made without departing from the spirit and scope of the invention as claimed.

I claim:

1. In a process for imparting to hydrophobic textile materials antistatic characteristics durable only to dry cleaning solvents, the steps of applying to said material an aqueous bath consisting essentially of a polymeric amino substituted ester dissolved in water, said ester being present in an amount of from about 1% to about 50% by weight of said bath, said ester essentially consisting of recurring radicals of at least one aliphatic dicarboxylic acid having from 4 to 10 carbon atoms, recurring radicals of an aliphatic compound bearing two hydroxyl radicals and selected from the group consisting of alkylene glycols and alkylene glycol ethers, and at least one amino radical selected from the group consisting of primary, secondary, and tertiary amino radicals attached directly to a carbon atom of a radical of an acid selected from the group consisting of aliphatic dibasic acids and aliphatic monobasic acids, said acid being esterified with the aforesaid aliphatic compound bearing two hydroxyl groups; and subsequently drying and heating the textile material having said bath arena-ea 9 applied thereto at an elevated temperature until said polymeric amino substituted ester imparts to said textile materials antistatic properties durable to dry cleaning solvents.

2. In a process as set forth in claim 1, said aliphatic dicarboxylic acid being selected from the group consisting of succinic, glutaric, methylsuccinic, and bis-(dimethylaminomethyl) succinic acid.

3. In a process as set forth in claim 1, said aliphatic compound being polyethylene glycol having a molecular Weight between substantially 200 and approximately 1540.

4. In a process as set forth in claim -1, said aliphatic compound being ethylene glycol.

5. In a process as set forth in claim 1, said aliphatic compound being 1,5 pentanediol.

6. In a process as set forth in claim 1, said aliphatic compound being diethylene glycol.

7. In a process as set forth in claim 1, said aliphatic compound being dipropylene glycol.

8. In a process as set forth in claim 1, said amino radical being the diethyl amino radical.

9. In a process as set forth in claim 1, said amino radical being the propyl amino radical.

10. In a process as set forth in claim 1, said amino radical being the unsubstituted amino group.

11. In a process as set forth in claim 1, said amino radical being the cyclohexylamino radical.

12. In a process as set forth in claim 1, said amino radical being the diethanolamine radical.

13. In a process as set forth in claim 1, acid being succinic acid.

14. In a process as set forth in claim 1, acid being phthalic acid.

15. In a process as set forth in claim 1, acid being crotonic acid.

16. In a process as set forth in claim 1, acid being acrylic acid.

17. In a process as set forth in claim 1, acid being methacrylic acid.

18. A textile material having antistatic characteristics durable only to dry cleaning solvents treated With a polymeric amino substituted ester essentially consisting of recurring radicals of at least one aliphatic dicarboxylic acid having from 4 to carbon atoms, recurring radicals of an aliphatic compound bearing two hydroxyl radicals and selected from the group consisting of alkylene glycols and alkylene glycol ethers and at least one amino radical selected from the group consisting of primary, secondary, and tertiary amino radicals attached directly to a carbon atom of a radical of an acid selected from the group consisting of aliphatic dibasic acids and aliphatic monobasic acids, said acid being esterified with the aforesaid aliphatic compound bearing two hydroxyl groups.

19. In a process for imparting to hydrophobic textile materials antistatic characteristics durable only to dry cleaning solvents, the steps of applying to said material an aqueous bath consisting essentially of a polymeric amino substituted ester essentially consisting of recurring radicals of at least one aliphatic dicarboxylic acid having from 4 to 10 carbon atoms, recurring radicals of an aliphatic compound bearing two hydroxyl radicals and selected from the group consisting of alkylene glycols and said esterified said esterified said esterified said esterified said esterified glycol ethers, and at least one amino radical selected from the group of primary, secondary, and tertiary amino radicals, said amino radical being attached directly to one of said carbon atoms and said dicarboxylic acid being esterified, said bath containing, by weight, from about 1% to about 50% of said polymeric amino substituted ester; and subsequently drying and heating the textile material having said bath applied thereto at an elevated temperature to impart to said textile material antistatic characteristics durable to dry cleaning.

20. In a process for imparting to hydrophobic textile materials antistatic characteristics durable only to dry cleaning solvents, the steps of applying to said material an aqueous bath consisting essentially of a polymeric amino substituted ester essentially consisting of recurring radicals of at least one dicarboxylic acid having from 4 to 10 carbon atoms, recurring radicals of at least one monocarboxylic acid having from three to four carbon atoms, recurring radicals of an aliphatic compound hearing two hydroxyl radicals and selected from the group consisting of alkylene glycols and glycol ethers, and at least one amino radical selected from the group of primary, secondary, and tertiary amino radicals, said amino radical being attached directly to one of the carbon atoms of said monocarboxylic acid, said dicarboxylic and said monocarboxylic acids being esterified With said aliphatic compound; and subsequently drying and heating the textile material having said bath applied thereto at an elevated temperature to impart to said textile material antistatic characteristics durable to dry cleaning.

21. A textile material having antistatic characteristics durable only to dry cleaning solvents treated with a polymeric amino substituted ester essentially consisting of recurring radicals of at least one dicarboxylic acid having from 4 to 10 carbon atoms, recurring radicals of at least one monocarboxylic acid having from three to four carbon atoms, recurring radicals of an aliphatic compound bearing two hydroxyl radicals and selected from the groupconsisting of alkylene glycols and alkylene glycol polyethers, and at least one amino radical selected from the group of primary, secondary, and tertiary amino radicals, said amino radical being attached directly to one of the carbon atoms of said monocarboxylic acid, said dicarboxylic and said monocarboxylic acids being esterified with said aliphatic compound.

22. In a process as set forth in claim 1, said amino radical being the methylamino radical.

23. In a process as set forth in claim 1, said amino radical being an alkyl imidazoline radical.

24. In a process as set forth in claim 1, said amino radical being the ethanolamine radical.

References Qited by the Examiner UNITED STATES PATENTS 2,417,513 3/47 Nelles et al 117-1395 3,063,870 11/62 Wakeman et al 117-139.5

WILLIAM D. MARTIN, Primary Examiner.

RICHARD D. NEVIUS, Examiner. 

1. IN A PROCESSFOR IMPARTING TO HYDROPHOBIC TEXTILE MATERIALS ANTISTATIC CHARACTERISTICS DURABLE ONLY TO DRY CLEANING SOLVENTS, THE STEPS OF APPLYING TO SAID MATERIAL AN AQUEOUS BATH CONSISTING ESSENTIALLY OF A POLYMERIC AMINO SUBSTITUTED ESTER DISSOLVED IN WATER, SAID ESTER BEING PRESENT IN AN AMOUNT OF FROM ABOUT 1% TO ABOUT 50% BY WEIGHT OF SAID BATH, SAID ESTER ESSENTIALLY CONSISTIG OF RECURRING RADICALS OF AT LEAST ONE ALIPHATIC DICARBOXYLIC ACID HAVING FROM 4 TO 10 CARBON ATOMS, RECURRING RADICALS OF AN ALIPHATIC COMPOUND BEARING TWO HYDROXYL RADICALS AND SELECTED FROM THE GROUP CONSISTING OF ALKYLENE GLYCOLS AND ALKYLENE GLYCOL ETHERS, AND AT LEAST ONE AMINO RADICAL SELECTED FROM THE GROUP CONSISTING OF PRIMARY, SECONDARY, AND TERTIARY AMINO RADICALS ATTACHED DIRECTLY TO A CARBON ATOM OF A RADICAL OF AN ACID SELECTED FROM THE GROUP CONSISTING OF ALIPHATIC DIBASIC ACIDS AND ALIPHATIC MONOBASIC ACIDS, SAID ACID BEING ESTERIFIED WITH THE AFORESAID ALIPHATIC COMPOUND BEARING TWO HYDROXYL GROUPS; AND SUBSEQUENTLY DRYING AND HEATING THE TEXTILE MATERIAL HAVING SAID BATH APPLIED THERETO AT AN ELEVATED TEMPERATURE UNTIL SAID POLYMERIC AMINO SUBSTITUTED ESTER IMPARTS TO SAID TEXTILE MATERIALS ANTISTATIC PROPERTIES DURABLE TO DRY CLEANING SOLVENTS. 